WO2006059692A1

WO2006059692A1 - Polyimide metal laminate and suspension for hard disk using same

Info

Publication number: WO2006059692A1
Application number: PCT/JP2005/022110
Authority: WO
Inventors: Koji Hirota; Naoki Nakazawa
Original assignee: Mitsui Chemicals, Inc.
Priority date: 2004-12-03
Filing date: 2005-12-01
Publication date: 2006-06-08
Also published as: JPWO2006059692A1; US20080268266A1; JP4384674B2; CN101065242A; CN101065242B

Abstract

Disclosed is a polyimide metal laminate wherein a copper foil and a stainless steel foil are formed on respective sides of a polyimide resin, or a stainless steel foil is formed on both sides of the polyimide resin. This polyimide metal laminate is characterized in that the peel strength between the stainless steel foil or copper foil and the polyimide resin is not less than 1.0 kN/m, the peel strength between the stainless steel foil or copper foil and the polyimide resin after thermally treating the polyimide metal laminate at 350˚C for 60 minutes is not less than 1.0 kN/m, and no swelling or deformation occurs in the polyimide metal laminate after the 60-minute heat treatment at 350˚C.

Description

Specification

Polyimide metal laminate and hard disk suspension using the same

[0001] The present invention relates to a polyimide metal laminate and a suspension for a node disk using the same, which are widely used for a flexible wiring board, a wireless suspension of a hard disk drive, and the like.

[0002] Specifically, polyimide is suitable for high-density circuit board materials because it has good heat resistance and has little change in properties after heat treatment, so that it can assemble components at high temperatures and can be processed ultrafinely. The present invention relates to a metal laminate and a suspension for a hard disk using the same.

Background art

[0003] At present, with so-called high-density hard disk drives, so-called wireless suspensions in which copper wiring is mainly formed directly on the suspension are used as suspensions for hard disk drives. As a material for this wireless suspension, a polyimide metal laminate made of copper alloy Z polyimide ZSUS304 is widely used.

[0004] As a method of manufacturing a wireless suspension using such a polyimide metal laminate, for example, Patent Document 1 discloses that after a predetermined pattern is applied to a copper alloy layer and a SUS304 layer, the polyimide layer is etched by plasma etching. A manufacturing method has been proposed in which the suspension is removed and the suspension is covered. Such a method using plasma etching has the advantage that the polyimide design having a fine shape is easy and the formation of flying leads is easy, so that the suspension design can be given freedom. . However, no consideration has been given to the thermal characteristics of the polyimide layer and the heat resistance of the metal laminate, and the high cover coat material required for connection to the board 'components and protection of copper wiring at high temperatures. For curing at a temperature, there were problems such as deformation of the polyimide layer and peeling of the copper wiring.

[0005] In order to improve the heat resistance and deformation described above, an attempt was made to reduce the linear humidity expansion coefficient of the polyimide layer to 15 X 10 "6Z% RH or less, which is disclosed in Patent Document 2. Although a certain effect on warping against humidity and dimensional stability has been achieved by keeping the tension coefficient low, no consideration has been given to the thermal stability of the high thermal expansion polyimide resin in contact with metal. The effect of the heat resistance as a metal laminate was sufficiently exhibited, but it could not be said.

Patent Document 1: Japanese Patent Laid-Open No. 9-293222

Patent Document 2: Japanese Patent Publication No. 2001-531582

Disclosure of the invention

Problems to be solved by the invention

[0006] In view of the above problems, an object of the present invention is to improve the heat resistance of a polyimide in contact with a metal, and to reduce the change in characteristics with respect to heat treatment, so that the polyimide metal laminate is heated. It is intended to provide a polyimide metal laminate excellent in heat resistance, and a suspension for a node disk using the same, by reducing the change in physical properties of the laminate with respect to the temperature change exposed to.

Means for solving the problem

As a result of intensive studies, the present inventors have controlled the thermal characteristics of polyimide in contact with metal, and use a specific physical property of polyimide in contact with stainless steel foil or copper foil when laminating polyimide onto metal. As a result, it was found that swelling and deformation after heating of the polyimide laminate were suppressed, and the present invention was completed.

That is, the present invention provides:

(1) The peel strength between the stainless steel foil and copper foil and the polyimide resin is l on the polyimide metal laminate with the copper foil and stainless steel foil on both sides of the polyimide resin and the stainless steel foil formed on both sides. The peel strength between the stainless steel foil and copper foil and the polyimide resin after the polyimide metal laminate is heat-treated at 350 ° C for 60 minutes is 1.0 kN / m or more. There is also a polyimide metal laminate characterized in that the deformability of the polyimide metal laminate after heat treatment at 350 ° C for 60 minutes, preferably,

(2) Polyimide resin in contact with stainless steel foil or copper foil has a glass transition temperature of 180 ° C or higher and a storage elastic modulus at 300 ° C of 1 X 10 ⁷ Pa to l X 10 ⁸ Pa, 350 The polyimide gold according to (1), wherein the storage elastic modulus at ° C is 2 × 10 ⁷ Pa to 2 × 10 ⁸ Pa A genus laminate, more preferably,

[0009] (3) The polyimide resin in contact with the stainless steel foil or copper foil is a polyimide obtained by reacting diamine with tetracarboxylic dianhydride, and the tetracarboxylic dianhydride used is , Pyromellitic dianhydride, 3, 3 ', 4, 4, -biphenyltetracarboxylic dianhydride at least one selected tetracarboxylic dianhydride, and 3, 3', 4, 4 '-Benzophenone tetracarboxylic dianhydride combined with 3, 3', 4, 4,-All of the tetracarboxylic dianhydrides used by benzophenone tetracarboxylic dianhydride 8 mole ^_0/0 or more and 20 mol% or less, as Jiamin further use, 1, 3- bis (3-amino Nofuenokishi) benzene, 4, 4, - bis (3-aminophenoxy) Bifue - le and, 1, 3-bis (3- (3-aminophenoxy) phenoxy) benzene, 2, 2- Bis [4- (4-aminophenoxy) phenol-] The polyimide metal laminate according to (1), which contains at least one kind of diamine selected for propane power,

[0010] (4) The polyimide metal laminate strength described in (1) to (3) relates to a hard disk suspension manufactured.

The invention's effect

[0011] According to the present invention, a high-density circuit board material that has good heat resistance of polyimide and little change in characteristics after heat treatment, enables component assembly at high temperatures, and enables ultrafine processing. A suitable polyimide metal laminate and a hard disk suspension using the same were provided.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the polyimide metal laminate of the present invention and the production method thereof will be described in detail.

In the polyimide metal laminate of the present invention, a stainless steel foil is formed on both sides or one side of a polyimide resin layer. A specific structure is a polyimide metal laminate in which a copper foil and a stainless steel foil are formed on both sides of a polyimide resin, or a stainless steel foil is formed on both sides. As the stainless steel foil, austenitic stainless steel such as SUS304, SUS301, or SUS305 can be used. Since the polyimide metal laminate of the present invention is suitably used as a suspension material, it is preferable to use one having panel characteristics. Preferably, SUS304 and SUS305 can be used. More preferably, SUS304 is hardened and In addition, SUS304H-TA material with tension annealing can be used.

[0013] As the metal that can be used in the polyimide metal laminate of the present invention, a copper foil can be used. Copper foil includes copper alloys containing copper as the main component and containing 50 wt% or more of the total weight of the alloy. As the copper foil, any type of electrolytic copper foil and rolled copper foil can be used. Any copper alloy foil can be used, including C7025 foil, which is an alloy with Ni, and HS1200 foil, which is an alloy with Sn. Since the laminate is suitably used as a suspension material, a copper alloy foil having panel characteristics can be preferably used. For example, C7025 foil and B52 foil manufactured by Nippon Olympus Co., Ltd., NK120 foil manufactured by Nikko Materials Co., Ltd., and EFTEC64-T foil manufactured by Furukawa Electric Co., Ltd. can be suitably used.

[0014] Since the copper foil used in the metal laminate is finely processed and may be used as wiring, it is preferable to thin the copper foil for fine wiring. Those having a thickness can be preferably used, and more preferably 12 / ζ πι to 1 / ζ πι.

[0015] There is no particular limitation on the thickness of the stainless steel foil used in the laminate, but as the recording density of hard disk drives (hereinafter abbreviated as HDDs) increases, the head needs to be as close as possible to the node disk. Yes. Therefore, the suspension material that supports the head is required to have softness, and the stainless steel foil also requires a thin film. Therefore, a thickness of 20 m to 10 m is preferably used, and 15 m to 10 m can be more preferably used.

[0016] The heat resistance of the polyimide resin layer of the polyimide metal laminate of the present invention is such that when heated in an oven at an ambient temperature of 350 ° C for 60 minutes, the polyimide resin layer and Z or polyimide resin It is necessary for the stainless steel foil or copper foil to swell and not peel off, that is, not to be deformed. It is preferable that swelling and peeling of 100 m or more do not occur. The polyimide metal laminate of the present invention is processed into a flexible wiring board or suspension, and when the chip slider is assembled onto the polyimide metal laminate, it may be exposed to a heating atmosphere of about 350 ° C. . It is also a force that is desired to prevent swelling and peeling at that time. In recent years, polyimide has been used as a cover material for polyimide metal laminates. Polyimide cover materials require high-temperature curing at 350 ° C, and polyimide metal laminates are also exposed to high temperatures due to curing. In this case, it is desirable that no swelling or the like occurs. The atmosphere in the oven is not limited, but is preferably an inert gas atmosphere such as nitrogen, Argon is better. This is because safety is ensured in the work. The ambient temperature is the temperature at which the polyimide metal laminate temperature is 350 ° C, and it is not necessary that the overall temperature in the oven be 350 ° C. It is preferable that swelling and peeling of 100 m or more do not occur during heating in the oven and after Z or after heating. However, the place where swelling and peeling occurs here is polyimide resin, polyimide resin and metal. It can occur at either the foil interface, and it must be free of any peeling, regardless of where it swells or peels off. As long as the size of the peeling is within a range that is preferably less than 100 m, there is no problem in appearance, but it is preferably less than 50 μm, more preferably less than 0.1 μm.

[0017] In the polyimide metal laminate of the present invention, the peel strength between the stainless steel foil and copper foil and the polyimide-based resin is l.OkN / m or more, and the viewpoint power for preventing wiring peeling after processing is also preferable. . In recent years, the miniaturization of processing has progressed, and fine wiring with a width of about 20 m is frequently processed. In order to increase the reliability in this fine wiring, it is preferable that the peel strength between the stainless steel foil, the copper foil, and the polyimide resin is higher, more preferably 1.2 kNZm or more. The measurement of peel strength is based on IPC-TM650, TypeA Sec2.4.9, and was performed on a 3.2 mm wide wiring.

[0018] Examples of the polyimide resin layer in the polyimide metal laminate of the present invention include polyimide and polyamideimide. Polyimide is preferable. Polyimide resin layer

Although it does not matter whether it is a single layer or multiple layers, 2 to 3 layers are preferred from the viewpoint of easy production and control of characteristics.

[0019] The polyimide-based resin in contact with the stainless steel foil or copper foil preferably has a glass transition temperature of 180 ° C or higher in order to ensure good adhesion to these metals. More preferably, it is 300 ° C. More preferably, it is 200 degreeC-270 degreeC. The glass transition temperature can be measured by a publicly known method.

[0020] The viscoelastic behavior of polyimide resin in contact with stainless steel foil or copper foil in the high temperature range of 300 ° C to 350 ° C has a great influence on the heat resistance characteristics of the polyimide metal laminate and the property changes after heating. Therefore, it is important to control the viscoelastic behavior in the high temperature region. A commercially available dynamic viscoelasticity measuring apparatus can be used for the measurement of viscoelastic behavior. Example For example, measurement can be performed using DMA Q800 manufactured by TI Instruments, RSA-2 manufactured by Rheometrics.

[0021] The storage elastic modulus behavior measured using a dynamic viscoelasticity measuring device in the high temperature region described above plays an especially important role in controlling the heat resistance characteristics of polyimide metal laminates and the property changes after heating. . The storage elastic modulus at 300 ° C is preferably lower as the storage elastic modulus, which preferably has high-temperature fluidity, in order to ensure adhesion to metal. However, if the storage modulus at 300 ° C is too low, problems such as excessive thermal deformation of the polyimide may occur when bonding metal and polyimide. In addition, if the polyimide metal laminate is heated while the polyimide absorbs water or immediately absorbs water, the swollen heat causes swelling in the polyimide. In order to suppress this, it is necessary to keep the storage elastic modulus of polyimide at a high temperature above a certain value. Specifically, it is necessary to have a storage elastic modulus larger than the saturated water vapor pressure at 300 ° C.

[0022] In order to obtain the above effect, the storage elastic modulus at 300 ° C of the polyimide in contact with the metal is preferably 1 X 10 ⁷ Pa to l X 10 ⁸ Pa, more preferably 7 X 10 ⁷ Pa to 9 X 1 0 ⁷ Pa.

[0023] The use of the polyimide metal laminate of the present invention includes HDD suspensions. A wiring circuit in which copper is etched is formed on the suspension. In recent years, as a cover material for protecting this wiring circuit, a cover material mainly composed of polyimide has been suitably used from the viewpoint of heat resistance and cleanliness. This polyimide cover material is indispensable as a process in which high-temperature curing of 350 ° C or higher is indispensable after the polyimide metal laminate is covered. In addition, components such as ICs and piezo elements are often mounted on the suspension. Even in this mounting, lead-free solder is used, and mounting at high temperatures is indispensable. For these reasons, it is necessary to control the heat resistance at 350 ° C of the polyimide layer in contact with the metal, that is, the storage elastic modulus that directly affects the heat resistance.

[0024] The storage elastic modulus at 350 ° C is higher than the saturated water vapor pressure at 350 ° C. It is preferable from the viewpoint of suppressing the thermal expansion, and the storage elastic modulus is low from the viewpoint of adhesion to metal. Is preferred. If the storage modulus of polyimide at 350 ° C is high, 350 ° C, 60 The adhesion between the polyimide and the metal after heating for a minute deteriorates, and the peel strength between the metal and the polyimide is less than 1. OkNZm, which is not preferable. Specifically, the storage elastic modulus of the polyimide at 350 ° C. is preferably 2 × 10 ⁷ Pa to 2 × 10 ⁸ Pa. More preferably, it is 3 × 10 ⁷ Pa to 1 × 10 ⁸ Pa. The polyimide resin that can satisfy these properties will be described below.

In addition, it is preferable that the peel strength between the stainless steel foil and copper foil and the polyimide resin after heat treatment of the polyimide metal laminate at 350 ° C for 60 minutes is 1.5 OkNZm or more 1.5 kNZm More preferably.

[0025] The polyimide resin in contact with the stainless steel foil or copper foil is preferably polyimide, and is preferably obtained by reacting diamine with tetracarboxylic dianhydride. The tetracarboxylic dianhydride used is pyromellitic dianhydride, 3,3 ', 4,4,'-biphenyltetracarboxylic dianhydride, at least one selected tetracarboxylic dianhydride And 3,3 ', 4,4, _benzophenonetetracarboxylic dianhydride, and from the viewpoint of ensuring the heat resistance of the polyimide, intramolecular and intermolecular amino groups and imine bridges It is preferable to contain 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, which is an acid dianhydride causing the reaction, at a certain ratio. However, when the acid dianhydride is used, the heat resistance becomes too high, and the storage elastic modulus of polyimide at a high temperature becomes too high, so that 3,3 ′, 4,4′-benzophenone tetracarboxylic acid is present. It is preferable that the acid dianhydride is 8 mol% or more and 20 mol% or less of the tetra force rubonic acid dianhydride used. More preferably, it is 10 mol% or more and 15 mol% or less. Also, any other acid dianhydride can be added within the range without impairing the properties of the thermoplastic polyimide.

The diamine used for the thermoplastic polyimide is 1,3-bis (3-aminophenoxy) benzene, 4,4, -bis (3-aminophenoxy) biphenyl, 1,3-bis (3- ( It is preferable to use at least one diamine selected from 3-aminophenoxy) benzene and 2,2-bis [4- (4-aminophenoxy) phenol] propane, but does not impair the properties of the polyimide. It is also possible to add any other diamine within.

[0027] When the polyimide described above is produced, the reaction molar ratio of the diamine component and tetracarboxylic dianhydride is in the range of 0.75 to 1.25, and the reaction is easily controlled, and the heat to be synthesized. 0.90 to 1.10 are more preferable because the heat flowability of the plastic polyimide is good. Thus, the polyimide resin manufactured by selecting the acid dianhydride and diamine as raw materials and also having a specific range force can satisfy the physical properties defined in the present invention.

[0028] The thickness of polyimide, like stainless steel foil or copper foil, can be reduced by reducing the thickness and weight of electrical equipment using polyimide metal laminates by 0.5 to 50 m. More preferably, it is 1 to 10 μm.

[0029] As the polyimide-based resin layer that is not in direct contact with the stainless steel foil or the copper foil, in addition to the thermoplastic polyimide resin described above, a commercially available non-thermoplastic polyimide film can be used. Avical (registered trademark) NPI manufactured by the company, Avical (registered trademark) HP, Kapton (registered trademark) EN manufactured by Toray DuPont Co., Ltd., etc. are preferably used. Also, any polyimide obtained by reacting diamine and tetracarboxylic dianhydride can be used within the range without impairing the properties of the polyimide metal laminate.

[0030] Examples of diamines that can be used include, for example, m-phenediamine, 0-phenediamine, p-phenediamine, m-aminobenzylamine, p-aminobenzylamine, bis. (3-aminophenyl) sulfide, (3-aminophenyl) (4-aminophenyl) sulfide, bis (4-aminophenol) sulfide, bis (3-aminophenol) sulfoxide, (3-aminophenol) -L) (4-aminophenol) sulfoxide, bis (3-aminophenyl) sulfone, (3-aminophenyl) (4-aminophenol) sulfone, bis (4-aminophenol) sulfone, 3, 3, -Diaminobenzophenone, 3, 4, -diaminobenzophenone, 4, 4, -diaminobenzophenone, 3, 3'-diaminodiphenenomethane, 3,4, -diaminodiphenenomethane, 4, 4, -diaminodiphenenomethane, 4, 4, -Diaminodiphenyl ether, 3, 3, -diaminodiphenyl ether, 3,4, -diaminodiphenyl ether, bis [4- (3-aminophenoxy) phenol] methane, bis [4- (4-aminophenol) phenol -L] methane, 1,1-bis [4- (3-aminophenoxy) phenol] ethane, 1,1-bis [4- (4-aminophenoxy) phenol] ethane, 1,2-bis [4 — (3-Aminophenoxy) phenol] ethane, 1,2-bis [4- (4-aminophenoxy) phenol] ethane, 2,

2-bis [4- (3-aminophenoxy) phenol] propane, 2,2-bis [4- (4-aminophenoxy) phenol] propane, 2,2-bis [4- (3-aminophenoxy) phenol -Le] butane, 2, 2-bis [

3— (3-Aminophenoxy) phenol] — 1, 1, 1, 3, 3, 3—Hexafnoreolov. Ronon, 2, 2— Bis [4- (4-aminophenoxy) phenol]-1, 1, 1, 3, 3, 3-hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1, 4-bis (3-aminophenoxy) benzene, 1,4, -bis (4-aminophenoxy) benzene, 4,4, -bis (3-aminophenoxy) biphenyl, 4,4, -bis (4-aminophenoxy) biphenyl, Bis [4- (3-aminophenoxy) phenol] ketone, Bis [4- (4-aminophenoxy) phenol] ketone, Bis [4- (3-aminophenoxy) phenol] sulfide, Bis [4- (4-aminophenoxy) phenol] sulfide, bis [4- (3-aminophenoxy) phenol] sulfoxide, bis [4- (aminophenoxy) phenol] sulfoxide, bis [4- (3-aminophenoxy) phenol -Lu] sulfone, bis [4- (4-aminophenoxy) phenol] sulfone, bis [4- (3-aminophenoxy) Si) Fuel] ether,

Bis [4- (4-aminophenoxy) phenol] ether, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 4 , 4, -Bis [3- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4, -bis [3- (3-Aminophenoxy) benzoyl] diphenyl ether, 4,4, -bis [4- (4 -Amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4, 4'-bis [4- (4-amino- at, a-dimethylbenzyl) phenoxy] diphenylsulfone, bis [4- {4- (4 -Aminophenoxy) phenoxy} phenol] sulfone, 1,4-bis [4- (4-aminophenoxy) -α, α-dimethylbenzen] benzene, 1,3-bis [4- (4-aminophenoxy)- α, α-Dimethylbenzyl] benzene, 1,3-bis (3- (4-aminophenoxy) phenoxy) benzene 1,3-bis (3- (2-aminophenoxy) phenoxy) benzene, 1,3-bis (4- (2-aminophenoxy) phenoxy) benzene, 1,3-bis (2- (2-aminophenoxy) Phenoxy) benzene, 1,3-bis (2- (3-aminophenoxy) phenoxy) benzene, 1,3-bis (2- (4-aminophenoxy) phenoxy) benzene, 1,4-bis (3- (3 -Aminophenoxy) phenoxy) benzene, 1,4-bis (3- (4-aminophenoxy) phenoxy) benzene, 1,4-bis (3- (2-aminophenoxy) phenoxy) benzene, 1,4-bis (4 -(2-Aminophenoxy) phenoxy) benzene, 1,4-bis (2- (2-aminophenoxy) phenoxy) benzene, 1,4-bis (2- (3-aminophenoxy) phenoxy) benzene, 1, 4- Bis (2- (4-aminophenoxy) phenoxy) benzene, 1,2-bis (3- (3-aminophenoxy) phenoxy) benzene, 1,2-bis (3- (4-aminophenoxy) phenoxy) benzene, 1,2-bis (3- (2-aminophenoxy) phenoxy) benzene, 1,2-bis (4- (4-Ami Nophenoxy) phenoxy) benzene, 1,2-bis (4- (3-aminophenoxy) phenoxy) benzene, 1,2-bis (4- (2-aminophenoxy) phenoxy) benzene, 1,2-bis (2- ( 2-aminophenoxy) phenoxy) benzene, 1,2-bis (2- (3-aminophenoxy) phenoxy) benzene, 1,2-bis (2- (4-aminophenoxy) phenoxy) benzene, 1,3-bis ( 3- (3-Aminophenoxy) phenoxy) -2-methylbenzene, 1,3-bis (3- (4-aminophenoxy) phenoxy) -4-methylbenzene, 1,3-bis (4- (3-aminophenoxy) ) Phenoxy) -2-ethyl benzene, 1,3-bis (3- (2-aminophenoxy) phenoxy) -5-sec-butylbenzene, [0032] 1,3-bis (4- (3-aminophenoxy) phenoxy) -2,5-dimethylbenzene, 1,3-bis (4- (2-amino-6-methylphenol) Xyl) phenoxy) benzene, 1,3-bis (2- (2-amino-6-ethylphenoxy) phenoxy) benzene, 1,3-bis (2- (3-aminophenoxy) -4-methylphenoxy) benzene, 1 , 3-Bis (2- (4-aminophenoxy) -4-tert-butylphenoxy) benzene, 1,4-bis (3- (3-aminophenoxy) phenoxy) -2,5-di-tert-butylbenzen, 1 , 4-Bis (3- (4-aminophenoxy) phenoxy) -2,3-dimethylbenzene, 1,4-bis (3- (2-amino-3-propylphenoxy) phenoxy) benzene, 1, 2 -Bis (3- (3-aminophenoxy) phenoxy) -4-methylbenzene, 1,2-bis (3- (4-aminophenoxy) phenoxy) -3-n-butylbenzene, 1,2-bis (3 -(2-amino-3-propylphenoxy) phenoxy) benzenebis (3-aminopropyl) tetramethyldisiloxane, Scan (10 Aminodekame styrene) tetramethyldisiloxane, bis (3-amino-phenoxyethanol methyl) tetramethyldisiloxane white hexane, and the like. These can be used alone or in admixture of two or more.

Examples of usable acid dianhydrides include pyromellitic dianhydride, 3-fluoropyromellitic dianhydride, 3,6-difluoropyromellitic dianhydride, 3, 6-bis ( Trifluoromethyl) pyromellitic dianhydride, 1, 2, 3, 4-benzenetetracarboxylic dianhydride, 2, 2 ', 3, 3, -benzophenone tetracarboxylic dianhydride, 3, 3, , 4, 4, -biphenyltetracarboxylic dianhydride, 3, 3 ", 4, 4 ,, -terphenyltetracarboxylic dianhydride, 3, 3 ,,,, 4, 4", -quaterhue -L-tetracarboxylic dianhydride, 3, 3 "", 4, 4 "', -kinkyl tetracarboxylic dianhydride, 2, 2', 3, 3, _biphenyltetracarboxylic dianhydride Anhydride, methylene-4,4, -diphthalic dianhydride, 1,1-ethylidene-4,4, -diphthalate Acid dianhydride, 2, 2-propylidene-4,4, -diphthalic acid dianhydride, 1,2-ethylene-4,4, -diphthalic acid dianhydride, 1,3-trimethylene-4,4,- Diphthalic acid dianhydride, 1,4-tetramethylene-4,4, -diphthalic acid dianhydride, 1,5-pentamethylene-4,4, -diphthalic acid dianhydride, 2,2-bis (3, 4-dicarboxyphenol) -1, 1, 1, 3, 3, 3-hexafluoropropani anhydride, difluoromethylene-4, 4, -diphthalic dianhydride, 1, 1, 2, 2 -Tetrafluoro mouth- 1,2-ethylene-4,4, -diphthalic dianhydride, 1, 1, 2, 2, 3, 3-hexafluo mouth- 1,3-trimethylene-4,4, -diphthalate Acid dianhydride, 1, 1, 2, 2, 3, 3, 4, 4 -Otafluoro- 1,4-teramethylene-4,4, -diphthalic dianhydride, 1, 1, 2, 2, 3, 3, 4, 4, 5, 5, decafluoro-1, 5-pentamethylene-4, 4, diphthalic dianhydride, oxy-4, 4, diphthalic acid Thio-4,4, -diphthalic dianhydride, sulfonyl-4,4, -diphthalic dianhydride, 1,3-bis (3,4-dicarboxyphenol) -1, 1, 3,3-tetramethylsiloxane dianhydride, 1,3-bis (3,4-dicarboxyphenyl) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenyl) benzene dianhydride 1, 3-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,3-bis [2- ( 3, 4-dicarboxyphenyl) -2-propyl] benzene dihydrate,

1,4-bis [2- (3,4-dicarboxyphenol) -2-propyl] benzene dianhydride, bis [3- (3,4-dicarboxyphenoxy) phenol] methane Anhydride, bis [4- (3,4-dicarboxyphenoxy) phenol] methane anhydride, 2,2-bis [3- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenol] propane dianhydride, 2,2-bis [3- (3,4-dicarboxyphenoxy) phenol -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenol] propane dianhydride, Bis (3,4-dicarboxyphenoxy) dimethylsilane dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) -1,1,3,3-tetramethyldisiloxane dianhydride, 2, 3, 6, 7-Naphthalenetetracarboxylic dianhydride 1, 2, 5, 6-naphthalene tetracarboxylic dianhydride, 3, 4, 9, 10-perylene tetracarboxylic dianhydride, 2, 3, 6, 7-anthracene tetracarboxylic dianhydride, 1 , 2, 7, 8-phenanthrenetetracarboxylic dianhydride, 1, 2, 3, 4-butanetetracarboxylic dianhydride, 1, 2, 3,4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexane-1, 2, 3, 4-tetracarboxylic dianhydride, cyclohexane-1, 2, 4, 5-tetracarboxylic dianhydride, 3, 3 ', 4, 4, -bicyclohexyltetracarboxylic dianhydride, carbo-4, 4, 4-bis (cyclohexane-1, 2-dicarboxylic acid ) Dianhydride, methylene-4,4, -bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-

4,4, -bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethylidene-4,4, -bis (cyclohexane-1,2-dicarboxylic acid) Anhydride, 2, 2-propylidene-4,4, -bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 1, 1, 1, 3, 3, 3-hexafluor 2-propylidene-4,4, -bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4, -bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, Thio-4,4, -bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfo-4,4, -bis (cyclohexane-1,2-dicarboxylic acid) dianhydride 2, 2, -Difluoro- 3, 3,, 4, 4, 4-biphenyl tetracarboxylic dianhydride, 5, 5, -Difluoro-3, 3, 4, 4, bi-biphenyl tetracarboxylic acid Dianhydride, 6, 6, -difluoro-3, 3, 4, 4, 4-biphenyltetracarboxylic Dianhydride, 2, 2,, 5, 5, 5, 6, 6, -hexafluoro-3, 3 ', 4, 4, -biphenyltetracarboxylic dianhydride, 2, 2, -bis (triflu Fluoromethyl) -3,3,4,4, -biphenyltetracarboxylic dianhydride 5,5, -bis (trifluoromethyl) -3,3,4,4, -biphenyltetracarl Boronic acid dianhydride, 6, 6, -bis (trifluoromethyl) -3, 3 ,, 4, 4, -biphenyl tetrahydride Rubonic acid dianhydride, 2, 2 ', 5, 5, -tetrakis (Trifluoromethyl) -3,3 ', 4,4, -biphenyltetracarboxylic dianhydride, 2, 2,6,6, -tetrakis (trifluoromethyl) -3,3' , 4,4, -biphenyltetracarboxylic dianhydride, 5,5,6,6, -tetrakis (trifluoromethyl) -3,3 ', 4,4, -biphenyltetracarboxylic dianhydride 2, 2 ', 5, 5', 6, 6, -hexakis (trifluoromethyl) -3, 3,, 4,4, -biphenyltetracarboxylic acid dianhydride, 3,3, -difluoroxy-4,4, -diphthalic dianhydride,

5, 5, -Difluorooxy-4,4, -diphthalic dianhydride, 6,6, -Difluoro-4,4, -diphthalic dianhydride, 3, 3 ,, 5, 5, 6, 6, 6, -Hexafluoroxy-4,4, -diphthalic dianhydride, 3, 3, -bis (trifluoromethyl) oxy-4,4, -diphthalic dianhydride,

5, 5, -Bis (trifluoromethyl) oxy-4, 4, -diphthalic dianhydride, 6, 6, -bis (tri Fluoromethyl) oxy-4,4, -diphthalic dianhydride, 3, 3 ,, 5, 5 tetrakis (trifluoromethyl) oxy-4,4, -diphthalic dianhydride, 3, 3 ,, 6, 6 tetrakis (Trifluoromethyl) oxy-4,4, -diphthalic dianhydride, 5, 5 ,, 6, 6, -tetrakis (trifluoromethyl) oxy-4, 4, -diphthalic dianhydride, 3, 3, 5, 5 ,, 6, 6, -Hexakis (trifluoromethyl) oxy-4,4, -diphthalic dianhydride, 3, 3, -difluorosulfol-4, 4, -diphthalic dianhydride, 5 , 5, -Difluorosulfol-4,4, -diphthalic dianhydride, 6,6, -Difluorosulfol-4, 4, -diphthalic dianhydride, 3, 3, 5, 5, 5, 6 , 6, -Hexafluorosulfol-4,4, -diphthalic dianhydride, 3, 3, -bis (trifluoromethyl) sulfol-4,4, -diphthalic dianhydride, 5 , Five -Bis (trifluoromethyl) sulfol-4,4, -diphthalic dianhydride, 6, 6, -bis (trifluoromethyl) sulfol-4,4, -diphthalic dianhydride 3, 3, 5, 5, 5, -tetrakis (trifluoromethyl) sulfol-4,4, -diphthalic dianhydride, 3, 3 ,, 6, 6, -tetrakis (trifluoromethyl) Sulfol-4,4, -diphthalic dianhydride, 5, 5, 6, 6, 6, -Tetrakis (trifluoromethyl) sulfol-4,4, -diphthalic dianhydride, 3, 3 ,, 5, 5, 6, 6, 6, -Hexakis (trifluoromethyl) sulfol-4,4, -diphthalic dianhydride, 3, 3, -difluoro-2,2-perfluoropropylidene-4 , 4, -diphthalic dianhydride, 5, 5, -difluoro-2,2-perfluoropropylidene-4,4, -diphthalic dianhydride, 6, 6, -difluoro-2,2- Perfluoropropylidene-4,4, -diphthal Acid dianhydride, 3, 3 ,, 5, 5, 6, 6, 6, -hexafluoro-2,2-perfluoropropylidene-4, 4, -diphthalic dianhydride, 3, 3, -bis (Trifluoromethyl) -2,2-Perfluoropropylidene-4,4, -diphthalic dianhydride, 5,5, -bis (trifluoromethyl) -2,2-perfluoropropylidene -4, 4, -diphthalic dianhydride, 6, 6, -difluoro-2,2-perfluoropropylidene-4, 4, -diphthalic dianhydride, 3, 3 ,, 5, 5, -Tetrakis (trifluoromethyl) -2,2-perfluoropropylidene-4,4, -diphthalic acid dihydrate, 3, 3 ,, 6, 6, -tetrakis (trifluoro) Methyl) -2,2-perfluoropropylidene-4,4, -diphthalic dianhydride, 5,5,6,6, -tetrakis (trifluoromethyl) -2,2-perfluoro Olopropylidene-4,4, -diphthalic dianhydride, 3, 3 ,, 5, 5 , 6,6, -Hexax (trifluoromethyl) -2,2-perfluoropropylidene-4,4, -diphthalic dianhydride, 9-phenol-9- (trifluoro) Methyl) xanthene-2,3,6,7-tetracarboxylic acid Water, 9, 9-bis (trifluoromethyl) xanthene-2, 3, 6, 7-tetracarboxylic dianhydride, bicyclo [2, 2, 2] oct-7-en-2, 3, 5, 6-tetracarboxylic dianhydride, 9, 9-bis [4- (3,4-dicarboxy) phenol] fluorene dianhydride, 9, 9-bis [4- (2, 3-di Carboxy) phenol] fluorene dianhydride and the like. These can be used alone or in admixture of two or more.

[0036] Synthesis of the polyimide-based resin generally includes N-methylpyrrolidone (NMP), methylformamide (DMF), dimethylacetamide (DMAc), dimethylsulfoxide (DMS O), dimethyl sulfate, In a solvent such as sulfolane, butyrolatatatone, cresol, phenol, halogenated phenol, cyclohexane, dixane, tetrahydrofuran, diglyme, triglyme, the tetracarboxylic dianhydride and the diamine are mixed at a predetermined ratio. Then, by reacting within a reaction temperature range of 0 ° C to 100 ° C, a polyimide resin precursor solution is obtained, and this solution is further heat-treated in a high temperature atmosphere of 200 ° C to 500 ° C. Thus, polyimide resin is obtained by imidization.

[0037] The polyimide metal laminate of the present invention can be produced by thermocompression bonding a polyimide resin and a metal foil. A method for thermocompression bonding of polyimide resin and metal foil is described. There is no restriction | limiting in particular about the method of thermocompression bonding. However, it is preferable to dry the polyimide moisture absorption to 0.1% ZRH or less before thermocompression bonding the polyimide resin and the metal foil. When thermocompression bonding is performed while moisture is absorbed, a metal laminate is formed in a state where moisture is contained in the polyimide, so that there is a problem that heating blistering is likely to occur in the polyimide. If the moisture absorption rate is 0.1% RH or less, the blistering does not occur and the characteristics are stabilized.

[0038] The method of drying the polyimide before thermocompression bonding is not particularly limited, but there is a method in which the polyimide is left to dry in an oven heated to 80 ° C or higher for a long time, for example, 10 hours or longer. Can be mentioned. There is also a method of drying polyimide using an IR heater or a heating roll. The moisture absorption rate can be measured by the Karl Fischer method or the Yanagi method by the thermogravimetric method.

[0039] Examples of the method for thermocompression bonding include a hot press method and a Z or heat laminating method as typical methods. As a heating press method, for example, polyimide resin and metal foil are cut into a predetermined size of a press machine, overlapped, and heated by a heating press. It can be manufactured by pressure bonding. The heating temperature is preferably 150 to 600 ° C. The pressing force is not limited, but it can be preferably produced at 0.1 to ⁵ OOkgZcm2. There is no particular limitation on the caloric pressure time.

[0040] The heat laminating method is not particularly limited, but a method of sandwiching and laminating between rolls is preferable. As the roll, a metal roll, a rubber roll, or the like can be used. Although there is no restriction | limiting in a material, Steel materials and stainless steel material are used as a metal roll. It is preferable to use a roll whose surface is treated with chrome plating or the like. As the rubber roll, it is preferable to use heat-resistant silicon rubber or fluorine rubber on the surface of the metal roll. The laminating temperature is preferably in the temperature range of 100 to 300 ° C. As the heating method, in addition to the conductive heating method, a radiation heating method such as far infrared, an induction heating method, or the like can be used.

[0041] It is also preferable to heat anneal after thermal lamination. A normal heating furnace, autoclave, etc. can be used as the heating device. Air, inert gas (nitrogen, argon), etc. can be used as the heating atmosphere. As the heating method, either the method of continuously heating the film or the method of leaving the film in the state of being left in the heating furnace is preferable. As the heating method, a conductive heating method, a radiant heating method, a combination method thereof, and the like are preferable. The heating temperature is preferably in the temperature range of 200 to 600 ° C. The heating time is preferably in the range of 0.05 to 5000 minutes.

In addition, the polyimide metal laminate of the present invention can be produced by applying a polyimide varnish precursor varnish to a metal foil and then drying. It can be produced by directly applying and drying a thermoplastic polyimide solution or a polyamic acid solution (hereinafter collectively referred to as varnish) which is a precursor of the thermoplastic polyimide on a metal foil. I can do it. A varnish is a solution obtained by polymerizing the specific diamine and tetracarboxylic dianhydride in a solvent.

[0043] As a method of directly coating on the metal foil, known methods such as a die coater, a comma coater, a roll coater, a gravure coater, a curtain coater, and a spray coater can be employed. It can be suitably used depending on the thickness to be applied, the viscosity of the varnish and the like.

[0044] As a method of drying and curing the applied varnish, an ordinary heating and drying furnace can be used. Air, inert gas (nitrogen, argon), etc. can be used as the atmosphere of the drying furnace. Dry As the temperature, a force range appropriately selected according to the boiling point of the solvent is preferably used. The drying time is appropriately selected depending on the thickness, concentration, and type of solvent, but it is desirable that the drying time be about 0.05 to 500 minutes.

[0045] According to the present invention, a polyimide metal laminate excellent in heat resistance can be obtained. Therefore, the polyimide metal laminate of the present invention is particularly suitably used as a hard disk suspension.

Hereinafter, the present invention will be described in more detail based on examples and comparative examples. The evaluation of various characteristics in the examples is based on the following method.

[Evaluation of heating blistering deformation]

A polyimide resin layer was formed on the metal foil to prepare a polyimide metal laminate. Next, the atmosphere temperature became 350 ° C! /, And it was introduced into Ruert oven (manufactured by Espec Co., Ltd.) and left for 60 minutes. Thereafter, the polyimide metal laminate is taken out with an inert oven, cooled to room temperature, the metal foil on one side is removed by etching, and the surface of the polyimide resin is swollen and peeled off with a 100-fold stereo microscope. It was confirmed whether it occurred or not (not deformed). In addition, when peeling was present, the magnitude of peeling was measured, and when there was a thing of 100 m or more, it was judged to be unacceptable.

[0047] [Measurement of peel strength]

The measurement was performed by a method based on IPC-TM-650, TypeA Sec2.4.9. The peel strength after heating (peel strength) was determined by preparing a peel strength test piece, leaving the test piece in an oven oven heated to 350 ° C for 60 minutes, and then cooling the test piece to room temperature. Measurements were taken.

[Measurement of storage modulus]

Measurement was performed in a tension mode using RSA-2 manufactured by Rheometrics. The heating rate was 3 ° C per minute, the measurement temperature was 100 ° C to 400 ° C, and the applied frequency was 1 Hz. Viscoelasticity analysis was performed to calculate the storage elastic modulus at 300 ° C and 350 ° C.

[Measurement method of glass transition temperature] Measurement was performed in a tensile mode using TMA-4000 manufactured by Bruker AXS. The heating rate was 10 ° C per minute and the measurement temperature was 100 ° C to 400 ° C. The polarization polarization of elongation at temperature was taken as the glass transition temperature.

[0048] Abbreviations of solvents, acid dianhydrides, and diamine used in Examples and the like are as follows.

DMAc: N, N, -dimethylacetamide

NMP: N-methyl-2-pyrrolidone

PPD: p-hue-rangeammin

ODA: 4,4, -Diaminodiphenyl ether

m-BP: 4,4, -Bis (3-aminophenoxy) biphenol

APB: 1,3-bis (3-aminophenoxy) benzene

APB5: 1,3-bis (3- (3-aminophenoxy) phenoxy) benzene

DABP: 3, 3,-Gaminobenzofuenone

TPE: 1,3-bis (4-aminophenoxy) benzene

p-BAPP: 2,2-bis [4- (4-aminophenoxy) phenol-propane] propane

BTDA: 3, 3 ,, 4, 4, -benzophenone tetracarboxylic dianhydride

PMDA: pyromellitic dianhydride

BPDA: 3, 3, 4, 4, 4-biphenyltetracarboxylic dianhydride

[0049] Synthesis Example 1

Synthesis of thermoplastic polyimide precursors>

Tetracarboxylic dianhydride and diamine listed in Table 1 were weighed and dissolved in 630 g of _DM Ac in a 1000 ml separable flask under a nitrogen stream. After dissolution, stirring was continued for 6 hours to carry out a polymerization reaction to obtain thermoplastic polyimide precursor varnishes A to D.

[0050] [Table 1]

[0051] Synthesis Example 2

The tetracarboxylic dianhydride and diamine described in Table 2 were weighed and dissolved in DMAc 630 g in a 1000 ml separable flask under a nitrogen stream. After dissolution, stirring was continued for 6 hours to carry out a polymerization reaction to obtain thermoplastic polyimide precursor varnishes E to I.

[0052] [Table 2]

Synthesis example 3

As the diamine components, 7.7 mol of PPD and 1.15 ^ / V, m-BP ^ l. 15 mol of ODA were weighed. As tetracarboxylic acid components, BPDA (5.4 mol) and PMDA (4.45 mol) were weighed. Dissolved and mixed in a mixed solvent of DMAc and NMP. The ratio of the solvents, the former 23 wt%, the latter 77 weight ⁰ /. Met. The viscosity of the resulting polyamic acid varnish was 25 ° C using an E-type viscometer. It was 30000cps, which was suitable for coating.

Example 1

On the commercially available stainless steel foil (manufactured by Nippon Steel Co., Ltd., trade name: SUS304H-TA, thickness: 20 m), each of the polyamic acid varnishes A to D in Synthesis Example 1 was applied as a thermoplastic polyimide layer. And dried. The thickness of the polyimide layer after coating and drying was 13 m. The drying conditions were 100 ° C, 150 ° C, 200 ° C, 250 ° C, 300 ° C, and heat treatment was performed stepwise for 5 minutes each. The stainless steel foil was removed by etching to obtain polyimide single layer films A to D. The dynamic viscoelasticity was measured by the method described above, and the storage elastic modulus at 300 ° C and 350 ° C was calculated. The results are shown in Table 3.

[0055] [Table 3]

Example 2

[0056] <Production of polyimide metal laminate>

On the commercially available copper alloy foil (made by Olin, trade name: C7025, thickness: 18 / zm), as a thermoplastic polyimide layer, each of the A to D polyamic acid varnishes of Synthesis Example 1 was applied and dried. Next, as the non-thermoplastic polyimide, the polyamic acid varnish of Synthesis Example 3 was applied and dried, and further, the A to D polyamic acid varnishes of Synthesis Example 1 were applied and dried, respectively, and single-sided polyimide metal laminate In addition, a laminate of commercially available stainless steel foil (manufactured by Nippon Steel Co., Ltd., trade name: SUS304H-TA, thickness 20 / zm) is laminated and thermocompression bonded to produce polyimide metal laminates A '' to D '' did. A rebar roll coater was used for the application of the polyamic acid varnish of Synthesis Example 1, and a die coater was used for the application of the polyamic acid varnish of Synthesis Example 3. The thickness of the polyimide layer after coating and drying was 2 m and 11 m, respectively. C, 150. C, 200. C, 250 ° C, 300. C, 350. Heat treatment was performed stepwise for 5 minutes at C. The thermocompression bonding conditions were 300 ° C, 50 kgf / cm ² , and 1 hour and 30 minutes. [0057] Evaluation of polyimide metal laminate>

Using the obtained polyimide metal laminate, the measurement was performed as described above for the blistering deformation, peel strength (peel strength), and peel strength (peel strength) after heating at 350 ° C. for 60 minutes. The results are shown in Table 4.

[0058] [Table 4]

Example 3

[0059] Manufacturing of double-sided adhesive sheet>

A to D of Synthesis Example 1 on both sides of a commercially available polyimide film (trade name: Apical (registered trademark) 12.5 NPI, thickness: 12.5 μπι) as a non-thermoplastic polyimide layer A polyamic acid varnish was applied and dried to prepare a double-sided adhesive sheet. A reverse roll coater was used to apply the thermoplastic polyamic acid varnish of Synthesis Example 1, and the total thickness of the polyimide layer after coating and drying was 18 m. The drying conditions were 100 ° C, 150 ° C, 200 ° C, 250 ° C, 300 ° C, and heat treatment was performed stepwise for 5 minutes each.

As a metal, copper alloy foil (made by Orin, trade name: C7025 (custom brand), thickness: 18 m) and stainless steel foil (made by Nippon Steel Co., Ltd., trade name: SUS304H-TA, thickness: 20 / X m) It was used. C7025 and SUS304H-TA foils laminated on a double-sided adhesive sheet are sandwiched between cushions (Kinyo Co., Ltd., product name: Kinkyo Board F200), and heated at 250 ° C and 70kgZcm ² Then, by pressure bonding for 60 minutes, a polyimide metal laminate A, "~!"', Which has a five-layer strength of SUS304H-TAZ thermoplastic polyimide Z non-thermoplastic polyimide Z Z thermoplastic polyimide ZC7025 was produced.

Using the obtained polyimide metal laminate, the blistering deformation, peel strength, and peel strength after heating at 350 ° C. for 60 minutes were measured as described above. The results are shown in Table 5. Example 2 When a polyimide metal laminate of ~ 3 is used as a hard disk suspension, a high-productivity and high-quality suspension is produced that does not show wiring separation even after curing of a cover material with good heat resistance of polyimide. It was possible.

[Table 5]

[0062] Comparative Example 1

On the commercially available stainless steel foil (manufactured by Nippon Steel Co., Ltd., trade name: SUS304H-TA, thickness: 20 μm), each of the polyamic acid varnishes of E to I in Synthesis Example 2 was applied as a thermoplastic polyimide layer and dried. Went. The thickness of the polyimide layer after coating and drying was 13 m. The drying conditions were 100 ° C, 150 ° C, 200 ° C, 250 ° C, 300 ° C, and heat treatment was performed stepwise for 5 minutes each. The stainless steel foil was removed by etching to obtain a polyimide single layer film Ε, ~ Γ. The dynamic viscoelasticity was measured by the method described above, and the storage elastic modulus at 300 ° C and 350 ° C was calculated. The results are shown in Table 6.

[0063] [Table 6]

[0064] Comparative Example 2

A polyimide metal laminate Ε ′ ′ to Γ ′ was produced and evaluated in the same manner as in Example 2 except that the thermoplastic polyimide precursors of E to I in Synthesis Example 2 were used as the thermoplastic polyimide. The results are shown in Table 7.

[0065] [Table 7] E "F" G "H" Γ

Heat swell, deformation Fail Pass Fail Pass Peel strength (kN / m) 1.5 1.2 1.4 0.7 0.8 Heat peel strength (kN / m) 2.1 0.5 1.9 0.7 1.3

[0066] Comparative Example 3

Except using the thermoplastic polyimide precursors of E to I in Synthesis Example 2 as the thermoplastic polyimide

In the same manner as in Example 3, polyimide metal laminates E ′ ′ ′ to Γ ′ ′ were produced and evaluated. The results are shown in Table 8.

[0067] [Table 8]

[0068] When the polyimide metal laminate of Comparative Examples 2 to 3 is used as a suspension for a hard disk, the polyimide is poor in heat resistance. However, it was hard to manufacture.

Industrial applicability

[0069] According to the present invention, it is possible to obtain a laminate plate capable of being subjected to ultrafine processing, and this can be applied to microfabricated products such as suspension materials for hard disk drives.

Claims

The scope of the claims

[1] The peel strength between the stainless steel foil and copper foil and the polyimide resin is high when the polyimide metal resin is formed with copper foil and stainless steel foil on both sides of the polyimide resin or stainless steel foil on both sides. l.OkN / m or more and the peel strength between the stainless steel foil and copper foil and the polyimide resin after the polyimide metal laminate is heated at 350 ° C for 60 minutes is l.OkN / m The polyimide metal laminate is characterized in that the polyimide metal laminate is not deformed after heat treatment at 350 ° C. for 60 minutes.

[2] Polyimide resin in contact with stainless steel foil or copper foil has a glass transition temperature of 180 ° C or higher and a storage elastic modulus at 300 ° C of 1 X 10 ⁷ Pa to l X 10 ⁸ Pa, 2. The polyimide metal laminate according to claim 1, wherein the storage elastic modulus at 350 ° C. is 2 × 10 ⁷ Pa to 2 × 10 ⁸ Pa.

[3] Polyimide resin in contact with stainless steel foil or copper foil is a polyimide obtained by reacting diamine with tetracarboxylic dianhydride, and the tetracarboxylic dianhydride used is Melitonic dianhydride, 3, 3 ', 4, 4'-biphenyltetracarboxylic dianhydride force at least one selected tetracarboxylic dianhydride, and 3, 3', 4, 4'- 8% by mole or more of all tetracarboxylic dianhydrides used by 3, 3 ', 4, 4'_benzophenone tetracarboxylic dianhydrides, combined with benzophenone tetracarboxylic dianhydrides Further, diamine to be used is 1,3-bis (3-aminophenoxy) benzene, 4,4 and bis (3-aminophenoxy) biphenyl, and 1,3-bis (3- (3-Aminophenoxy) phenoxy) benzene, 2, 2-bis [4- (4-a Nofuenokishi) Hue - Honoré] polyimide metal laminate according to claim 1 selected propane force is intended to include at least one Jiamin.

[4] A suspension for a hard disk produced by the polyimide metal laminate strength according to any one of claims 1 to 3.